Dyestuff mixture



Patented Sept. 1, 1936 UNITED STATES PATENT OFFICE DYE STUFF MIXTURE Joachim Mueller, Ludwigshafen-on-the-ltlnnc, Germany, assignor to General Aniline Works. Inc., New York, N. Y., a corporation of Delaware No Drawing. Application January 21, 1935, Serial No. 2,842. In Germany January 27, 1934 Claims. (Cl. 8-6) The present invention relates to mixtures of dyestuff mixtures not only vat dyestuffs but also dyestuffs. other dyestufls, as for example azo dyestufis, It is already known that n many cases dyestuffs dyestuffs suitable for dyeing wool, leuco esters of are employed not alone but in mixtures with other vet dye tuffs basic d estuffs or Substantive 5 dyestuffs. It had been observed that the fastness Stufis may be empioyed properties of such mixtures of dyestuffs are fre- It dyestufl mixtures consisting wholly f e quently not so valuable as could be expected with dyestuiis are employed the d tufl are mixed regard to the fastness properties of the single dyegetheibef r their use and then vetted in the stuffs present in the mixture. Quite to the'conusual manner It iS also possible to mix the trary it occurs in most cases that dyeings obtained Stuffs in the form of their vets. If beside vet f example b employing mixture? dyeetufis dyestuffs other dyestuffs which are not injured having a relatively little fastness with dyestuffs by reducing agents are present in the mixture the of great fastness when exposed to to the vat dyestuffs can be vatted in the presence of the atmosphere and to other influences show an unsaid other dyestiifle If dyestufis are present in me favorable behaviour because the dyestuff having the mixture which are injured by reducing agents. the better fastness properties is destroyed so that one can proceed by first dyeing the fabric to be only the shade of the less valuable dyestufi dyed with the desired vat dyestuifs and then dyemains. In other c it Occurs that the ing it in a second operation with any desired other stuff having arelatively little fastness is destroyed dyestufis as for example with acid, basic or So t a theresulting Shade of dyeing a stantive dyestufis or development dyestuffs. In mates the shade of t dyestufi haVmg the better cases when the components of the development fastness. Beside even mixtures of dyestufis dyestuffs are not affected by the action of the having practically the same good fastness propingredients of the vet they may he hroueht'en 25 erties show 8- m l change-0f Shade due to to the fabrics together with the vat dyestuffs, the the fact that the PreBence of one dyestufi dyeings then being developed. Instead of the vatfaVOrS the destruqtion of e ether dyestufi Pres dyestuffs their stable leuco compounds as for exent in the mixture. In each case, a considerable empietheir sulfuric acid estefs may he empieyed Chan e Of Shade takes place- In this manner vegetable as well as animal fibres 30 I have now found that dyestufi mixtures in may be dyed, shades of excellent fastness propwhich at lea t One dyestufi of the 'azabehzah' erties being obtained. Even when employing relthrone series is present which contains at least etiveiy smaii amounts of the said vat dyestufis of one acridine ring beside the azabehzanthmne the azabenzanthrone series as for example 10 part of the K101601116, not only in contrast to per cent thereof dyeings are pbtained the fastness 35 other dyestuff mixtures yielding the same shade, properties of which are remarkably hetter than do not show the said disadvantages but alsoare it could be expected regarding the iastness molten distinguished by an especially favorable behaviour ties of the cc,mpenente This efieet is espeeiaiiy upon exp to light, to the atmosphere and evident if mixtures are employed which contain to othe infillencesat least 20 per cent of the said vat dyestuffs of the 40 Dyestuffs of the azabenzanthrone series of the azabenzanthmne Series said kind suitable for the purpose of the present The foiiowing examples-win further, illustrate inven are, for example, described in the the nature of this invention but the invention is application 663548 and the Brim-15h not restricted to these examples. The parts are 45 'specificationNo. 421,264. Substitution products by weiehh i of these dyestuffs, as for example their derivatives containing halogen atoms or alkyl, alkoxy, amino Example 1 or acyl amino groups, may also be employed with t e the same result. As the other components of the 5 parts of 8-azabenzanthrone-alpha-am1noanthraquinone are mixed with 10 parts of the dyestufi corresponding to the formula:

5 The mixture is introduced into 10000 parts of water and 50 parts of sodium hydroxide and parts of sodium hydrosulfite are added thereto. 500 parts of cotton are then treated with the vat thus obtained at 60 C. for one hour. The cotton is then washed with water and exposed to the air. When the oxidation is. completed, the cotton is soaped'in the usual manner. The dyeing thus obtained shows abeautiful green shade of a high degree of fastness to light and the atmosphere.

Instead of the said azabenzanthrone dyestufl its dichloro, dibromo or its alkyl derivatives may be employed. Furthermore, the corresponding dyestufis obtainable from 5- or B z3-azabenzanthrone may be used. If desired the proportions COIIIH O or to the British specification No. 231,532, the formula o NH-C0-CO-NH or the red vat dyestufi according to tllile German Patent No. 239,094 corresponding to t e formula of the two dyestuffs may be varied within wide or Indanthrene Golden Orange G (Schultz Farbstofi-Tabellen, 7th edition, No. 1245) or Brilliant Indigo B. A. S. F. 4B (ibid., No. 1314) or Indanthrene Brilliant Violet BBK (ibid, No. 1222) or I-Iydrone Blue R (ibid, No 1111) or Indanthrene Olive R (ibid, No. 1224) may be employed.

The mixing of the dyestuffs may also first take place in the vat. Furthermore the corresponding stable derivatives of the leuco compounds of the said vat dyestuffs, as 'for example their leuco sulfuric esters and similar compounds, may be mixed before employment or in the dyebath,'the dyeing being carried out in the usual manner.

It is is desired to prepare a mixed dyeing while Example 2 Cotton is dyed in the usual manner with thevat dyestufi of the azabenzanthrone series employed in Example 1 and the resulting dyeing is overdyed with a basic dyestuff as for example Auramine 0 (ibid, No. 752) or the yellow azo dyestufi derived from diazotized dehydrothiotoluidine sulfonic carboxylic acid and aceto-acetic acid anilide. Dyeing's are obtained which are distinguished by a very good fastness to light.

If it is desired to over-dye with a developer dyestufi, the resulting dyeing is slop-padded with a suitable coupling component, as for example di-(acetoacetyl) -tolidide, the dyeing being developed in the usual manner, as for example by treatment with a solution of diazotized orthochloraniline.

Example 3 5 parts of 8-azabenzanthrone-alpha-aminoanthraquinone are mixed with 7 parts of anthraquinone diphenyl thiazole corresponding to the formula:

' CoHs'(% A The mixture is introduced into 10000 parts of water and 50 parts of sodium hydroxide and 15 parts of sodium hydrosulfite are added thereto. 500 parts of cotton are then treated with the vat thus obtained at C. for one hour. The cotton is then washed with water and exposed to the air. When the oxidationis completed, the cotton is soaped in the usual manner. The dyeing thus obtained shows a beautiful green shade of a high degree of fastness to light and the atmosphere.

Instead of ,the said azabenzanthrone dyestuif its dichloro, dibromo or its alkyl derivatives may be employed. Furthermore, the corresponding dyestufls obtainable from 5 or Bz3-azabenzanthrone may be used. If desired the proportions of the two dyestuffs maybe varied within wide limits, dyeings' of excellent fastness always being obtained.

Instead of the dyestufi indicated by the formula as above, the dyestuffs mentioned in the third paragraph of Example 1 may be employed.

Example 4 3 parts of 8-azabenzanthrone-alpha-aminoanthraquinone are mixed with 8 parts of the dyestuff corresponding to the formula:

The mixture is introduced into 10000 parts of water and 50 parts of sodium hydroxide and 15 parts of sodium hydrosulflte are added thereto. 500 parts of cotton are then treated with the vat thus obtained at 60 C. for one hour. The cotton is then washed with water and exposed to the air. When the oxidation is completed, the cotton is soaped in the usual manner. The dyeing thus obtained shows a beautiful green shade of a high degree of fastness to light and the atmosphere. 1

Instead of the said azabenzanthrone dyestuff its dichloro, dibromo or its alkyl derivatives may be employed. Furthermore, the corresponding dyestuffs obtainable from 5- or Bz3-azabenzanthrone may be used. If desired the proportions of the two dyestuffs maybe varied within wide 5 limits, dyeings of excellent fastness always being obtained.

Insteadof the dyestufi indicated by the formula as above, the dyestuffs mentioned in the third paragraph of Example 1 may be employed.

Example 20 parts of the sodium salt ofthe sulfuric acid ester of leuco-B-azabenzanthrone-alpha-aminoanthraquinone are mixed with parts of the sodium salt of the sulfuric acid ester of leuco-afi- 5 dibromdibenzpyrenequinone. The said mixture is then dissolved in 1000 parts of water. Into the solution there are introduced 30 parts of cotton while adding 10 parts of sodium nitrite and 50 parts of anhydrous sodium sulfate. After 45 minutes, the cotton is squeezed and introduced into a solution of 35 parts of 96 per cent sulfuric acid in 1000 parts of water. There is obtained a yellowish olive-green dyeing of very high fast- ;5 ness to light and the atmosphere.

The following table contains a number of dyestufi mixtures in order to further illustrate the present invention. The parts (by weight) of the dyestufis mentioned are calculated on 10000 parts 50 of the dyebath to be used.

Dyestufl of the aizabenzanthrone ser es Other dyestuiis 6 parts of the yellow dyestufl 65 2 parts of B-azabenzanthroneobtainable according to the alpha-aminoanthraquinone.

1.8 parts of Bz3-azabenzanthronealphwaminoanthraqumone.

2nd paragraph of Example 1 70 of the German Patent No.

1.2 parts of dichlor-B-azabenzan- 3parts oi anthraquinonediphethrone-alpha-aminoanthranyldithiazole. quinone.

0.32 part of S-azabenzanthrone- 1.2 parts of 5.5'-dl(benzoylammo)- 1.1'-anthrlmide-oarbazole.

alpha-aminoanthraquinone.

2nd paragraph of Example 1 Dyeetufl of the azabenzanthrone series Other dyestufis 0.4 part of dlbrom-8-azabenzanthrone-elpha-aminoanthraquinone.

3.75 parts of S-azabenzanthronealpha-aminoanthraquinone. 1.8 parts of 8-azabenzathronealpha-aminoanthraquinone.

3 parts of S-azabenzanthi-onealpha-aminoanthraquinone.

5 parts ol S-azabenzanthronealphaemmoanthraquinone.

3 parts of BzS-azabenzanthronealpha-aminoanthraquinone.

2.5 parts of S-azabenzanthronealpha-aminoanthraquinone.

5parts of 8-azabenzanthronealpha-aminoanthraquinone.

4 parts of B-azabenzanthronealpha-aminoanthraqumone.

I 5.5 parts of Bz3-azabenzanthronealpha-aminoanthraquinone.

5.4 parts of S-azabenzanthronealpha-aminoanthraquinone.

5 parts of S-azahenzenthronealphaaminoanthraquinone.

5 parts of S-azabenzanthronepyrazolanthrone.

1 part of the brown vat dyestufl.

according to the first paragraph of the Example of the U. S. Patent 1,804,538 and 0.2 part of 5.5'-di(benzoylamino)- l.1'-anthrimide-carbazole.

4 parts of Algol Orange RF (Schultz Farbstoif-Tabellen, 7th edition, No. 1349).

18 garts of the yellow dyestufl o tainable according to the 1 Example 4 of the U. S. Patent 3.5 parts of Indanthrene Red Violet RH. (Schultz Farbstofl- Tabellen, 7th edition, No.-l354) 1.5parts oi thedyestufi employed in Example 1 of this application.

5 parts of Indanthrene Gold Orange G (Schultz Farbstofl- Tabellen, 7th edition, No. 1245).

6 parts of Anthra Red RT (Schultz Farbstofi-Tabellcn, 7th edition, No. 1254).

7.5 partsoi Indanthrene Brilliant Violet RR (Schultz Farbstofl- Tabellen, 7th edition, No

1265). 2 parts of Indanthrene Brilliant Pink R (Schultz Ferbstofl- Tabellen, 7th edition, No.

7.5 parts of Indanthrene Currant RK (Schultz Farbstofl-Tabellen, 7th edition, No. 1226).

3 parts of Indanthrene Brown R (Schultz Farbstofi-Tabellen, 7th edition, No. 1227).

4 parts of Indanthrene Orange RRK (Schultz Farbstofi-Tabellen, 7th edition, No. 1225).

2.3 parts of Indanthrene Brown R (Schultz Farbstofi-Tabellen, 7th edition, No. 1227) and 2.5 parts of Indanthrene Olive R (Schultz Farbstofi-Tabellen, 7th edition, No. 1224).

5 parts of Hydrone Blue B (Schultz Farbstoff-Tabellen, 7th edition, No. 1113).

7.5 parts of the brown vat dyestuil obtainable according to the German patent No. 241,910, page 3, line 14.

3.2 parts of the yellow vat dyestufi obtainable according to the 2nd paragraph of Example 1 of the German Patent No.

251,350. 4 parts of the blue vat dyestufi according to Example 1 of the U. S. Patent No. 1,207,982.

4 parts of the black vat dyestufl according to the U. S. Patent No. 1,452,805.

3 parts of Indanthrene Brilliant Pink R (Schultz Farbstofl- 'labellen, 7th edition, No.

What I claim is:

one other vat dyestuif.

3. Dyestufi mixtures containing at least one dyestuff of the azabenzanthrone series which contains at least one acridine ring beside the azabenzanthrone part of themolecule selected from the group consisting of azabenzanthrone-alphaaminoanthraquinones, their homologues and halogen derivatives and at least one other organic dyestui'f the latter being insensitive to reducing agents.

4. Dyestuif mixtures containing at least one dyestufi 'of the azabenzanthrone series which contains at least one acridine ring beside'the azabenzanthrone part of the molecule selected from the group consisting of azabenzanthrone-alphaamlnoanthraquinones, their homologues and hal- 8. The dyestufl' mixture containing 8-azabenzanthrone-alpha-aminoanthraquinone and anthraquinonediphenylthiazole.

9. The dyestufl mixture containing 8-azabenzanthrone-alpha aminoanthraquinone and the dyestufi corresponding to the formula:

ogen derivatives and atleast one other vat dyestufl.

5. Dyestuff mixtures containing anazabenzanthrone-alpha-aminoanthraquinone which -may be halogenated, and anthraquinonediphenyldithiazole which corresponds to the formula:

0 S-C-CaEi I I I 6. Dyestufl mixtures containing amazabenzanthrone-alpha-aminoanthraquinone which may be halogenated, and the dyestufl corresponding to thetormula:

:10. The dyestuflf mixture containing 8-azaben- 'zanthrone-alpha-aminoanthraquinone and the dyestufl corresponding to the formula:

'7. Dyestufl mixtures containing an azabenzanthrone-alpha-aminoanthraquinone which may be halogenated, and the dyestufl. corresponding to the formula: v V 

